Method for the preparation of polyether acetic acids



Patented Dec. 30, 1952 METHOD FOR THE PREPARATION O F POLYETHER ACETIC ACIDS Kurt Hofer, Basel, Switzerland, assignor to Sandoz A. G., Basel, Switzerland, a Swiss firm No Drawing. Application August 29, 1949, Serial No. 113,023. In Switzerland September 1, 1948 Claims.

According to the conventional art, compounds containing ether groups are produced by interaction of the corresponding alkali metal a1- coholates with esters of inorganic acids, for inaryl or heterocyclic radical which may be interrupted. by hetero atoms or hetero atom groups,

2 which radical can also be substituted in any way, but in particular by hydroxyl groups and A represents an alkylene radical containing 2 to 4 carbon atoms wherein R--O-A can also be stance according to the following equation: 5 part of a ring system, to react with a mono- R O alkali metal+ha1ogen--R':R,O--R'+a1- haloacetic acid, a salt or a functional derivkali metal halide. ative of the same gs: fisg g gz gggg 32 33323223 g E: The following compounds can suitably be used action of alkali metals High-molecular alcohols accordmg to tms mventlon as ether alcohols: hardly react with alkali metals and there is Alkyl cycloalkyl amlkyl' aryl and amlkylglywl therefore, often an alcoholate of a lower alcohol 3 33 gggf g igg 21 35 2 32 1? 2 2351 11 23;} produced first which is subsequently caused to d i da d 1 t d h react with the high-molecular alcohol. Metha cyc ods have also become known according to which 15 methylcyclohexyl benzyl phenyl'ethyl phenyl the anhydrous alcoholates are obtained from alamylphenyl octylphenylglycol and polyglycol cohols by interaction with alkalimetal hydroxides ig i ii i polypropylei-e under the action of heat, while removing the "g 5 1 g; {1 3 g fi and water i the reaction in a1 Suitable by e e alk ali r net l hy d l ox id -a ddition comg f distillation (ct German I Patent pounds of the ether alcohols are formed on mixfiiiih g fffi gfi igz i gi g m the alkali metal hydroxide, particularly sorather large excess of alcohol, a great deal of 2123 figf gigfifi gg x iig 22: Egg: heait andfiften gives rise to undeshfed 2a tion compounds react very easily with mono.- 2323 2 gga ggfig i g ggz gg gg gzgfi 9 haloacetic acid or its salts and its functional side-reactions render this metho d unsuitable for derimfives respectively and this one-n already the preparation of alcoholates of high molecular gg gg fi fig figfigf :3 1: iggs i ggg fg 328 581 gg i ig g 1 5 2 5 and methods the alcohol or ether alcohol must be ads havse breen g b g Si 253 5 g gg used in large excess or a suitable diluent will be ether acetic acids, as for preparing compounds small and is not necessary in many cases;

a I c I y c alcohols used as starting materials can mostly gaug methods Whlch have hlthelw become react only with difiiculty with alkalijmetals and the method with alkali metal hydroxide, with (1 slmpllclty 0f BXecut10n Plant removal of the water by azeotropic idistmation, (2) No side-reactions and thus moreased purity very easily causes side-reactions -and cannot be 40 Of W pl'Pducts carried out at all with high molecular ether al- Hlgh ylelds cohols' (4) No or only an insignificant consumption of A simple method has now been found for pre- BY Daring polyethel' acetic acids, salts thereof or Simple method for etherlf ymg hlgh molec functional derivatives of the same, that is to say Illa? ether Whlch the Processes compounds containing at least two ether-like which have hltherto been known cannot be bonded oxygen atoms in the molecule. Dlflyed y d y S0 V ifig ggg t; gii gggz gy 3 32; The following examples, without being limi itative, illustrate the resent invention. 7 metal hydroxide-addition compound of an ether p alcohol of the general fo m l vEaxmtple 1.-2-ethylbutomy-ethoxy-acettc ac d R O A OH CHa-CHz wherein R represents an alkyl, cycloalkyl, aralkyl, fiCHCHFO'CgHLO CHCO on I 5 GHs-C 2 To 600 grams of Z-ethylbutylglycol ether grams of powdered sodium hydroxide were added with vigorous stirring and slight cooling. The temperature increased up to 50 C. After cooling down to 25 C. 195 grams of monochloroacetic acid were slowly added. during the addition the temperature did not surpass 60 C. At the end the mixture was kept at 40-50 C. for a further hour and then the excess of 2-ethylbutylglycol ether distilled off in vacuo. sulphuric acid was then added to the still warm distillation residue whereby the raw 2-ethylbutoxyethoxy-acetic acid was separated, which is a light brown, oily liquid. The pure acid can be obtained by distillation in vauco; B. P. at 12: 169.5 to 171 C. The yield was 90% of the theory.

Ewample 2.-Buto:cyethomyethowyacetic acid C4H9OC2H4OC2H4OCH2COOI-I By using, in Example 1, the same amount of n-butoxy-ethoxyethanol of the formula:

instead of 2-ethylbutylglyool ether and causing the same to react in the same way, as described in Example 1, with sodium hydroxide and monochloroacetic acid the butoxyethoxyethoxyacetic acid, B. P. 15: 195 to 200 C. was obtained in a more than 90% yield.

Example 3. Tetrahydrofurfuryloxyacetic acid To 3 moles of tetrahydrofurfuryl alcohol were added 2 moles of powdered sodium hydroxide with stirring and moderate, cooling. The temperature increased from to 45 C. After cooling down to 20 C. 1 mole of monochloroacetic acid was slowly added whereby care had be taken that the temperature did not exceed 55 C. With a view to complete the reaction, the reaction Care was taken that 5 Example 4.-Lauryloxyethoazyethem/acetic acid ethoxyacetic acid and common salt. The product was very easily soluble in water and formed strongly foaming solutions which showed a marked wetting effect beside being lime-stable. By treating with sulphuric acid the free acid could be obtained.

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4 Example 5 .1 :3 dz (butoasyethoxy) -propyl-2- omyacetic acid CiH O C2H4O CHz-CHCH O C2H4O C4110 0 Q1120 0 on 1 3-di- (butoxyethoxy) -2-oxyp ropane was reacted with sodiumhydroxideand chloracetic acid and worked up as described in Example 1. The 1 :3-di- (butoxyethoxy) -propyl-2-oxyacetic acid, B. P. 1: 175 to 180 C. was thus obtained.

Example 6 To 160 grams of the molten ether obtained by the addition of two moles of ethylene oxide into one mole of technical cetyl alcohol, there were added 22 grams-of powdered sodium hydroxide. The whole was mixed keeping the temperature at 40 to C. A turbid and viscous solution was obtained, to which were added 130 grams of the sodium salt of monochloracetic acid, the temperature having been kept at 50-60 C. After all the acid had been added, the mixture was stirred for three hours at 50 C. and one further hour at 75 C.

The excess of the sodium hydroxide was neutralized with sulphuric acid. After cooling, there was obtained a clear, waxy like mass, which was spray-dried. The dried product constituted an easily soluble powder, which can be used as a detergent.

Example 7 To 21.5 grams of the ether of the-formula:

osa1-- cezorrgo son there were stirred in first 25 grams of powdered sodium hydroxide and afterwards. grams of the sodium salt of monochloracetic acid, the term perature having been kept at 40 to 50 C. The reaction product was then stirred for two hours at 50 C. and finally for one hour at C. There was obtained a clear, viscous mass, which became turbid as sodium chloride was precipitated. It was clearly soluble in water and its aqueous solutions had good wetting and foaming properties.

What I claim is:

1. Aprocess for the manufacture of poly er derivatives of acetic acid, comprising the step of reacting a compound of the formula ROA.OH.MeOI-I wherein R denotes a hydrocarbon radical, A denotes a member selected from the group consisting of alkylene and alkylene-O-alkylene, the alkylene in each case, being lower alkylene, and wherein Me denotes an alkali metal, with a compound of the formula X CH2 COOY wherein X denotes halogen and Y means a cation including hydrogen.

2. A process for the manufacture of polyether derivatives of acetic acid, comprising the step of reacting a compound of the formula X CH2 COOY wherein X denotes halogen and Y means a cation including hydrogen.

3. A process for the manufacture of polyether derivatives of acetic acid, comprising the step of reacting a compound of the formula wherein Me denotes an alkaline metal, with a compound of the formula X CH2 COOY wherein X denotes halogen and Y means a cation including hydrogen.

4. A process for the manufacture of polyether derivatives of acetic acid, comprising the step of reacting a compound of the formula wherein Me denotes an alkaline metal, with a compound of the formula X CH2 COOY wherein X denotes halogen and Y means a cation including hydrogen.

5. A process for the manufacture of polyether derivatives of acetic acid, comprising the step of reacting a compound of the formula X CH2 COOY wherein X denotes halogen and Y means a cation including hydrogen.

KURT HOFER.

REFERENCES CITED 10 The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 15 554,938 Lederer Feb. 18, 1896 2,068,905 Bruson Jan. 26, 1937 2,083,482 Steindorfi et a1. June 8, 1937 2,210,874 Balle et al Aug. 13, 19 0 2,333,726' Leibitz-Piwnicki et al. Nov. 9, 1943 20 2,458,741 Schmerling Jan. 11, 1949 2,474,175 Weizmann June 21, 1949 2,480,817 Warren Aug. 30, 1949 2,490,109 Weizmann Dec. 6, 1949 2,493,126 Foster et al Jan. 3, 1950 25 FOREIGN PATENTS Number Country Date 679,711 Germany Aug. 15, 1939 

1. A PROCESS FOR THE MANUFACTURE OF POLYETHER DERIVATIVES OF ACETIC ACID, COMPRISING THE STEP OF REACTING A COMPOUND OF THE FORMULA 